Bisymmetrical aryl polyhydroxy alkyl ethers



wetting agents, etc.

United S res atent 3,135,806 BISYMMETRICAL ARYL POLYHYDROXY ALKYL ETHERSRobert Steckler, Chagrin Falls, Ohio, Jesse Werner,

This invention relates to a new class of bisymmetrical aryl polyhydroxyalkyl ethers which are useful per se and as intermediates in thepreparation of a diversified number of new and useful chemical products.1

We have discovered that bisymmetrical phenolic compounds obtained by thecondensation of monohydric or polyhydric phenols with polyalkoxy acetalsare readily reactive with alkylene oxides and alkylene carbonates toyield bisymmetrical aryl polyhydroxy alkyl ethers which are useful perse, and which may be sulfated or sulfonated to yield water-solublesurfactants i.e., detergents, In addition, they may be reacted withisocyanates to form novel and useful polyurethanes. They may also bereacted with monoand/ or poly-functional acids, i.e. saturated orunsaturated to yield a new and interesting class of polyesters and alkydresins.

The bisymmetrical phenolic compounds which are reacted with an alkyleneoxide or alkylene carbonate in accordance with the present invention arecharacterized by a structure corresponding to the following generalformula:

RO-CH Ll.lm

CH3 wherein A represents an aryl group such as phenyl, di phenyl,naphthyl or anthracyl, R represents an alkyl radical of 1 to 5 carbonatoms, m represents a positive integer of from 2 to and n represents apositive integer 'to form 1 to 3.

prepared by the reaction of a vinyl alkyl ether with a lower alcohol.The higher polyalkoxy acetals wherein m ranges from 2 to 30 are obtainedby condensing 1 mole -of an alcohol such as methanol, ethanol, propanol,

butanol, etc. with 2 to 30 moles of a vinyl methyl ether, vinyl ethylether, vinyl propyl ether, vinyl butyl ether,

etc.

3,135,806 Patented June 2, 1964 ice As illustrative of such polyalkoxyacetals, the following may be mentioned:

1,1,3,5-tetramethoxy hexane l,l,3,5-tetraethoxy hexane,1-diethoxy-3,5-dimethoxy hexane ,1,3,5,7-pentamethoxy octane,1,3,5,7,9-hexamethoxy decane ,1,3,5,7,9,1l-heptamethoxy dodecane,1,3,5,7,9,11,13-octamethoxy tetradecane ,l,3-trimethoxy-5-ethoxy hexane,l-dimethoxy-3,5-ethoxy hexane ,1-dimethoxy-3,5,7-ethoxy octane Higherpolyalkoxy acetals obtained by condensing 1 mole of lower alcohol with10-30 moles of vinyl alkyl ether.

It is to be further noted that a mixture of two or more of the foregoingspecific polyalkoxy acetals may be condensed with a monoor poly-hydricphenol. The ratio of the polyalkoxy acetals constituting the mixture isimmaterial, as only 1 molecular equivalent thereof will condense with 2molecular equivalents of the monoor polyhydric phenol.

The monohydric or polyhydric phenols which are condensed with theforegoing polyalkoxy acetals include phenol, 0-, m-, and p-cresol, ethylphenol, isopropyl phenol, butyl phenol, tertiary butyl phenol, hexylphenol, octyl phenol, nonyl phenol, decyl phenol, dinonyl phenol,dodecyl phenol, tridecyl phenol, diisobutyl phenol, 3- pentadecylphenol, stearyl phenol, 2,4- and 3,5-xylenol, cardanol, ocandfi-naphthols, 2- and 9-hydroxy anthracene, 1,8-dihydroxyanthranol,orcinol, catechol, pyrocatechol, resorcinol, methyl resorcinol,pyrogallol, 4,4- dihydroxydiphenyl, 1,5-dihydroxy naphthalene, and thelike. It is to be noted that cardanol is a technical grade of anacardolhaving the formula:

I OH

oisfinv wherein the C side chain contains two double bonds and islinear.

From a visual inspection of the generic formula of the bis-phenoliccompounds utilized in accordance with the present invention, it will benoted that the aryl nuclei characterized by A are joined by a carbonatom bearing a polyalkoxy alkane chain as a substituent instead of theconventional alkane chain ranging from 1 to 5 carbon atoms. The presenceof the polyalkoxy alkane chain in the bis-phenol compounds of thepresent invention provides the new and unexpected property of impartingto the bis-phenols greatly improved compatibility with polar typechemicals, increased reactivity with lower aldehydes, alkylene oxidesand alkylene carbonates.

In preparing the foregoing bis-phenolic compounds, 2 moles of amonohydric or polyhydric phenol are condensed with 1 mole of apolyalkoxy acetal under the usual'reaction conditions. As catalyst, wehave found that acids such as sulfuric acid, phosphoric acid,chloracetic acid, dichloracetic acid, trichloracetic acid,trifluoracetic acid, fluoboric acid, hydrochloric acid, alkane sulfonicacids, aryl sulfonic acids, etc., may be employed. The catalystconcentration and temperature of reaction should be such as to eliminatepossible side reactions. In other words, .there is a relationshipbetween the reactivity of the monohydric or polyhydric phenol and thereaction conditions employed. Very reactive phenols such as phenol,resorcinol, phloroglucinol and the like will react rapidly with thepolyalkoxy acetals in the presence of dilute acids and mild temperaturessuch as 35-50 C. Less reactive phenols such as o-cresol, 2,4 and3,5-xylenols, 2-anthrol and 1,5-dihydroxy naphthalene and the like arebest reacted at or near reflux by employing a strong concentration of anacid such as will not cause sulfonation of the resulting product therebydiminishing the yield. Under such circumstances, instead of theinorganic acids, alkyl or aryl sulfonic acids are preferred. The acidswhich may be used include among others:

Trifluoracetic acid Fluoboric acid Hydrochloric acid Alkane sulfonicacids. 'Aryl' sulfonicacids Sulfuric acid Phosphoric acid Chloraceticacid Dichloracetic acid Trichloracetic acid The bisymmetrical arylpolyhydroxy alkyl ethers prepared in accordance with the presentinvention while employing the foregoing bisymmetrical phenolic compoundsand alkylene oxides or alkylene carbonates are characterized by thefollowing general formula:

wherein A, R, m and n have the same values as given above and Rrepresents either hydrogen, methyl or ethyl and x represents a positiveinteger of from 1 to 40. The length of the alkyloxy or polyalkoxy chaincharacterized by x will be dependent upon the number of moles of eitheralkylene oxide or alkylene carbonateemployed.

This may range from 1 to 40 moles or higher ofalkylene oxide or alkylenecarbonate for each hydroxyl group present in the bis-phenolic compound.The addition of the alkyloxy or polyalkoxy chains to the bis-phenol compound is carried out by conventional alkoxylation procedures asdescribed in United States Patents 1,970,578; 2,213,477; 2,575,832;2,593,112 and 2,676,975, the disclosures of which are incorporated byreference thereto as illustrative of such procedures. Since the additionof the alkylene oxide such as ethylene oxide, 1,2-propylene oxide or1,2-butylene oxide or the corresponding carbonates such as ethylenecarbonate, 1,2-propylene carbonate or 1,2-butylene carbonate is readilyfollowed in the alkoxylation reaction byobserving the weight increasesof the reaction mixture, any number of moles of the alkylene oxide oralkylene carbonate can be added: The bi symmetrical phenolic compoundand the alkylene oxide or alkylene carbonate are simply heated at atemperature ranging from about 110 to 200, C. in the presence of analkali such as sodium or potassium hydroxide or sodium or. potassiumcarbonate fora-period of time until the desired number of moles ofalkylene oxide or alkylene carbonate have been added. As an alternative,according to conventional procedures, the alkoxylation reaction may becontinued until a 1% solution of'the resulting product is homogenenousin water at a temperature of about 40 C. The, point at which thesolution becomes non-homogeneous or cloudy is called the cloud point.

The following'examples, which are merely illustrative, will show thepreparation of several types of the new class of bisymmetrical arylpolyhydroxy alkyl ethers. All parts given are by weight. I j

In a three-necked flask equipped with stirrer, thermometer'and refluxcondenser there were added, while maintaining a temperature of 55-60 C.,106 parts of glacial acetic acid, 106 parts of sulfuric acid .of -98%concentration, 54 parts of a mixture consisting of 90% The mixture wasthen heated at C5 for 17 hours.

At the start of the reaction, evolution of carbon dioxide caused foamingwhich slowly abated as reaction went to completion. The cooled reactionmass was then thoroughly washedwith water in a Waring Blendor and thendried. The resulting resin is hard, brittle and non-caking at roomtemperature. and methyl ethyl ketone but insoluble in aqueous caustic.

In a three-neck flask equipped with stirrer, and'thermometer there wereadded 53 parts of sulfuric acid of 40% concentration and 12 parts ofresorcinol. stirring was continued and then addedv dropwise were 15parts of 1,1,3,5,7pentaethoxyoctane over a period of 25- 30 ininuteswhile maintainingthe temperature between 3540 C... Stirring wascontinued for an additional 30 minutes and the reaction mixture allowedto stand overnight, then neutralized with 10% aqueouscausticsoda whichresultedin a clear, stable solution. Addition of carbon dioxide gave aprecipitation which was separated by washing with water and drying.

An intimate mixture was'prepared consisting of 100 7 parts of theforegoing dried bis-phenol compound, 90

parts of 1,2-propylene carbonate and'4 parts of 'potassium carbonate.The mixture was then heatedat C. for

18 hoursi At the start of the reaction, evolution of carbon dioxidecaused foaming which slowly abated asthe reactionwent to completion. Thecooled reaction mass was then thoroughly washed with Water in a WaringBlendor and then dried. The resulting. resin is hard,

brittle, and non-caking at room temperature. It is soluble It is stillsoluble in acetone The in acetone and methyl ethyl ketone, but insolublein aqueous caustic.

Example III To a three-necked flask equipped with stirrer, thermometerand heat source there were charged at 44 C., 24 parts of phloroglucinol,42.4 parts of sulfuric acid of 95-98% concentration and 63.6 parts ofwater. While the phloroglucinol is not completely soluble in the mixturenevertheless it is suspended in solution. To the reaction mixture isadded slowly dropwise during 20 minutes 30 parts of1,1,3,5,7-pentamethoxy octane while maintaining the temperature at 40 C.Shortly thereafter a very stiff resin is formed. After standingovernight the resin is soluble in 20% aqueous sodium hydroxide and wasprecipitated with carbon dioxide gas.

An intimate mixture was prepared consisting of 70 parts of the abovebis-phenol compound, 89.6 parts of 1,2-butylene carbonate and 4 parts ofpotassium carbonate. The mixture was then heated at 120 C. for 18 hours.At the start of the reaction, evolution of carbon dioxide caused foamingwhich slowly abated as the reaction went to completion. The cooledreaction mass Was then thoroughly washed with water with a WaringBlendor and then dried. The resulting resin is hard, brittle andnon-caking at room temperature. It is soluble in acetone and methylethyl ketone but insoluble in aqueous caustic.

Example IV H(OCH1CH3) O (OH2OHgO)mH HC-O CH l. .l2

CH3 50 parts of the bis-phenol prepared in accordance with Example I wasdissolved in aqueous sodium hydroxide solution and the mixture treatedwith 134 parts of ethylene oxide at 180 C. The cloud point of theresulting product was approximately 50 C.

Example V (OC z Dm? l s z 10 Ira-00H, l .l ls

To a 3-necked flask equipped with stirrer, thermometer and refluxcondenser there were added 424 parts of com mercial grade concentratedsulfuric acid (95-98%) and 424 parts of glacial acetic acid with coolingto maintain the temperature at 50 C. To this was then added 188 parts ofphenol dissolved in 10% by weight of water. After the latter mixture hadbeen stirred for a period of a few minutes, there was then added 568parts of a polymethoxy acetal obtained by condensing 10 moles ofvinylmethyl ether with 1 mole of methanol dropwise over a 30 minuteperiod while maintaining the temperature between 5560 C. The reactioncontent was stirred for an additional 50 minutes and then allowed tostand overnight.

25 parts of the above reaction mixture was dissolved in 5% aqueouscaustic to give a clear amber solution. The solution was then treatedwith 31 parts of ethylene oxide at 180 C.

The first part of Example 11 was repeated with the exception that 15parts of 1,l,3,5,7-pentaethoxy octane were replaced by 1.5 parts of apolyethoxy acetal obtained by condensing 30 moles of vinyl ethyl etherwith 1 mole of ethanol. The reaction mixture was allowed to standovernight and then neutralized with 10% aqueous caustic soda to yield aclear stable solution.

The solution containing parts of the bis-phenol was treated with 11.1parts of ethylene oxide at 180 C.

Example VII Example II was repeated with the exception that 12 parts ofresorcinol were replaced by 15 parts of a-naphthol. One hundred parts ofthe resulting bis-phenol compound was dissolved in 10% aqueous sodiumhydroxide solution.

The foregoing alkaline solution was then treated with 95 parts ofethylene oxide at 180 C.

Example VIII Example I was repeated with the exception that 24 parts ofphloroglucinol were replaced by 30 parts of Z-anthrol. After completion,the reaction mixture was allowed to stand overnight, then neutralizedwith 10% aqueous caustic soda.

The foregoing caustic soda solution was treated with parts of1,2-propylene oxide at a temperature of C.

The products of the foregoing examples are resinous in nature and areespecially adaptable for the preparation of varnishes, lacquers, enamelsand electrical insulating mediums by conventional procedures. They arealso useful in the preparation of molding compositions. The fillermaterial which is usually wood flour, is uniformly impregnated with asolution of the resin in acetone or methyl ethyl ketone, equal parts ofresin and filler being normally employed. The mixed product is dried toeliminate the solvent and then ground. The ground material is thenmolded in the conventional manner. Solutions of the resins in acetone ormethyl ethyl ketone 7 8 v and further diluted with alcohols are veryuseful in im- 3, A compound having the following formula: pregnatingsheets of paper, cloth, etc., which are to be OH OH pressed together'toform stiff sheets and blocks. g i i t All of the foregoing bisymmetricalaryl polyhy'droxy- HBO*H CH OHi- HCH3 alkyl ethers are readily sulfatedand sulfonated by con- 5 3 ventional means to yield a new class ofwater-soluble H OH products useful as detergents, emulsifiers, wettingagents, I H g and the mm H;C-HGCH1-O C 0 0H, ET-OH;

It is to be noted that monoethers of the bis-phenol com- I ""i "lpounds, utilized in accordance with the present invention, can beobtained by adding corresponding chlorohydrins HC-OCZHE to thebis-phenols in the presence of alkali. I This application is acontinuation-in-part of our pend- CH8 ing application Serial No.764,231, filed September 30, 4. A compound having the following formula:

on on V V HaoH,0Hc--H,C0- o-om-n-om-cm CH I T [0 a 1 n H C-H CH( JHaO$ 27 C 1958, for Bisymmetrical Phenolic Compounds, now 5. A compound havingthe following formula: United States Patent 3,061,650. w OH) 0 g OCH CHO H ,Each of the products prepared in accordance with the z 2 w 2 a )10foregoing examples was found to be an excellent tanning agent. Tanningis effected by milling the skin at a pH of 2-9 with the agent. g

We claim: 1 g v 1. A compound having the following general formula: 75

H a R1 HOOCH3 (H[OCHCH2]:-O) -ACA-(O[CH:CH O IXH) i L-t- EH2 6. Acompound having the following formula: I; H m I i Z zMn o 0H,cH,o ,,H

0H, wherein A represents an aryl group selected from the classconsisting of phenyl, naphthyl, and anthracyl, R represents an alkylradical of 1 to 5 carbon atoms, R represents a member selected from theclass consisting of 5 hydrogen, methyl and ethyl groups, m represents aposi- 4 l 0H tive integer of from 2 to 30,.n represents a positiveinteger Y 3 of from 1 to 3, and x representsa positive integer of CHfrom 1 to 40. v a

2. A compound having the following formula: 7. A compound having thefollowing formula:

HO-CHa-CH2C| O-CHz-CIEH-OH 7 H(OOHzOH3)1--O (|)(CH,OH O) H O 0 11ooHioH2 i-0 oomommnz F"??? g n l HCOCH EC-OO H L |3 a L Ja '11, 7 CHReferences Cited in the file of this patent UNITED STATES PATENTS2,454,541 Bock et a1; Nov. 28, 1948 2,504,064 Bock et a1. Apr. 11, 1950,

1. A COMPOUND HAVING THE FOLLOWING GENERAL FORMULA: